Optimization of performance and composition for glass ceramics prepared from mixing molten slags
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摘要: 以電爐鎳鐵渣和普通高爐渣為主要原料，采用Petrurgic一步法制備了微晶玻璃，并結合力學性能測試，對樣品進行了X射線衍射(XRD)、掃描電鏡(SEM)等分析，討論了電爐鎳鐵渣和普通高爐渣配比、Mg2+含量以及晶核劑TiO2對成品微觀結構及性能的影響規律.結果表明：將熔渣冷卻至900℃結晶和650℃退火，能夠制備出性能優良的微晶玻璃.當Mg2+含量增加且析出晶體為單一輝石族礦物時，微晶玻璃具有較高的力學性能.電爐鎳鐵渣或Mg2+含量增加，會導致其輝石族礦物含量增加，當兩種渣混合摻量達到90%(鎳鐵渣質量分數50%，高爐渣質量分數為40%)且外摻2% MgO時，所制備微晶玻璃結構致密，僅含有單一輝石族礦物，包括透輝石、普通輝石和斜頑輝石，從而具有最優的力學性能，其抗折強度達210 MPa，抗壓強度達1162 MPa.電爐鎳鐵渣或者MgO含量進一步增加，會導致鎂橄欖石析出，此時微晶玻璃的力學性能顯著下降.TiO2含量的增加不改變微晶玻璃晶體種類，合適摻入TiO2(本實驗為質量分數2%)能夠增強透輝石含量，提升性能；但過量摻入會抑制晶體生長，導致其性能下降.Abstract: The direct preparation of materials from high-temperature slag is an effective way for the integrated utilization of slags and their thermal energy. In this paper, with ferronickel slags and blast furnace slags as the main raw materials, glass ceramics were prepared by the Petrurgic method, a one-step heat-treatment method by direct crystallization of the slag melt during its cooling process. The ratio of ferronickel slags and blast furnace slags, Mg2+ content, and the effect of nucleating agent TiO2 on the microstructure and properties of the products were analyzed by X-ray diffraction, scanning electron microscopy, and mechanical property test. The results show that glass ceramics with excellent properties can be prepared by crystallization at 900℃ and annealing at 650℃ for slag melts during the cooling process. When the content of Mg2+ increased, and the precipitated crystal was a single-pyroxene-group mineral, the glass ceramics exhibited the highest mechanical properties. The content of pyroxene group mineral increased with the increasing ferronickel slag or MgO content. When the content of the two slags reached 90% (50% ferronickel slags and 40% blast furnace slags) with the addition of 2% MgO, the prepared glass ceramics presented a compact structure containing single-pyroxene-group minerals, including diopside, ordinary pyroxene, and clinopyroxene, and the best mechanical properties with flexural strength of 210 MPa and compressive strength of 1162 MPa. However, the further increase in ferronickel slag or MgO content led to the precipitation of forsterite, which significantly deteriorated the mechanical properties of glass ceramics. The increasing content of TiO2 caused no change in the type of crystals in the glass ceramics. Appropriate doping (2% in the experiments) increased the content of diopside, but excessive doping inhibited the crystal growth and reduced its performance.
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Key words:
- ferronickel slags /
- blast furnace slags /
- glass-ceramic /
- pyroxene group /
- forsterite
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圖 1 微晶玻璃不同制備工藝比較.(a)成核溫度和析晶溫度區域極少疊加下的溫度與成核/晶體生長速率變化關系; (b)兩步法熱處理制度；(c) 成核溫度和析晶溫度區域大部分疊加的溫度與成核/晶體生長速率變化關系；(d) Petrurgic法熱處理制度
Figure 1. Comparison of different heat treatment processes of glass ceramics: (a) temperature dependence of the nucleation and growth rates with negligible overlap; (b) two step method; (c) temperature dependence of the nucleation and growth rates with significant overlap of the secondary nuclei rate and the growth rate curves; (d) Petrurgic method
圖 2 不同爐渣摻量樣品性能測試. (a)抗折強度；(b)抗壓強度
Figure 2. Performance of samples with different slag contents: (a) flexural strength; (b) compressive strength
圖 3 不同Mg2+含量樣品性能測試.(a)抗折強度；(b)抗壓強度
Figure 3. Performance of samples with different Mg2+ contents: (a) flexural strength; (b) compressive strength
圖 4 不同TiO2含量樣品性能測試. (a)抗折強度；(b)抗壓強度
Figure 4. Performance of samples with different TiO2 contents: (a) flexural strength; (b) compressive strength
圖 5 樣品X射線衍射分析. (a)不同爐渣摻量樣品的X射線衍射比較，其中箭頭表示特征峰的位置；(b)純礦物單晶相X射線衍射峰比較
Figure 5. XRD analysis of the samples: (a) comparison among different samples (the arrows indicate the positions of characteristic peaks); (b) XRD comparison among pure minerals
圖 6 樣品X射線衍射分析. (a)不同Mg2+含量樣品的X射線衍射比較，其中箭頭表示特征峰的位置；(b)純礦物單晶相X射線衍射峰比較
Figure 6. XRD analysis of sample: (a) XRD comparison among samples with different Mg2+ contents (the arrows indicate the positions of characteristic peaks); (b) XRD comparison among pure minerals
圖 7 樣品X射線衍射分析. (a)不同TiO2含量樣品的X射線衍射比較，其中箭頭表示特征峰的變化趨勢；(b)純礦物單晶相峰X射線衍射比較
Figure 7. XRD analysis of samples: (a) XRD comparison among samples with different TiO2 contents, the arrows indicate the positions of characteristic peaks; (b) XRD comparison among pure minerals
圖 8 不同爐渣摻量樣品掃描鏡圖. (a)S1;(b)S2;(c)S3
Figure 8. SEM images of the samples with different slag contents: (a)S1;(b)S2;(c)S3
圖 9 不同Mg2+含量樣品掃描電鏡圖. (a)S2;(b)S4;(c)S5
Figure 9. SEM images among samples with different Mg2+ contents: (a)S2;(b)S4;(c)S5
圖 10 不同TiO2含量樣品掃描電鏡圖. (a)S1;(b)S6;(c)S7
Figure 10. SEM images of the samples with different TiO2 contents: (a)S2;(b)S4;(c)S5
表 1 樣品化學組成(質量分數)
Table 1. Chemical composition of samples?
% 樣品 高爐渣 電爐鎳鐵渣 石英砂 MgCO3 TiO2 CaO SiO2 Al2O3 MgO TiO2 Fe2O3 其他 S1 50 40 10 20.39 45.06 9.98 16.42 0.47 5.48 2.2 S2 40 50 10 16.71 46.87 8.79 18.23 0.40 6.60 2.4 S3 30 60 10 13.02 48.68 7.60 20.05 0.33 7.71 2.61 S4 40 50 10 2① 16.38 45.95 8.62 19.84 0.39 6.47 2.35 S5 40 50 10 4① 16.07 45.07 8.45 21.37 0.38 6.35 2.31 S6 50 40 10 2 19.99 44.18 9.78 16.10 2.42 5.37 2.16 S7 50 40 10 4 19.61 43.32 9.60 15.79 4.30 5.27 2.11 注：①和②表示換算后的MgO質量分數. 
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表 2 樣品與國標要求性能的對比
Table 2. Comparison between performance of different samples and requirement of standard
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表 3 熔渣改質顯熱和補熱對比
Table 3. Contrast between sensible heat and heat compensation of slag
樣品 熔渣顯熱，Qs/J 改質劑吸熱，Qen/J 50%高爐熔渣+40%鎳鐵電爐熔渣+10%冷態石英砂 26928 10320 40%高爐熔渣+50%鎳鐵電爐熔渣+10%冷態石英砂 24480 10568 30%高爐熔渣+60%鎳鐵電爐熔渣+10%冷態石英砂 18360 11193 40%高爐熔渣+50%鎳鐵電爐熔渣+10%冷態石英砂+外加2%MgO 18348 14479
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